Method for patterning a photoresist material wherein an anti-reflective coating comprising a copolymer of bisphenol A and benzophenone is used

ABSTRACT

A co-polymer of benzophenone and bisphenol A has been shown to have DUV absorption properties. Therefore, the co-polymer has particular utility as an antireflective coating in microlithography applications. Incorporating anthracene into the co-polymer backbone enhances absorption at 248 nm. The endcapper used for the co-polymer can vary widely depending on the needs of the user and can be selected to promote adhesion, stability, and absorption of different wavelengths.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of application Ser. No. 08/281,398filed Jul. 27, 1994, U.S. Pat. No. 5,607,824.

DESCRIPTION BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention is generally related to antireflective coatings used inmicrolithography processes and, more particularly, to an antireflectivecoating with that has light absorbing properties at deep ultraviolet(DUV) wavelengths.

2. Description of the Prior Art

Microlithography is directed to the formation of micron and sub-micronsized patterns on substrates such as semiconductor chips and wafers.Forming patterns of these small dimensions is quite difficult. Often,the surface of the substrate underlying the photoresist will haveimperfections and the non-uniformity of the surface, which can sometimesbe grainy or have a plurality of undulations, will result in the resistlayer having a variable thickness across the surface of the substrate.The uneven topography of the underlying substrate may have variations inheight of the same approximate magnitude as the light which is beingused to image the photoresist material. Most photoresists aretransparent to DUV radiation. Thus, when the photoresist is beingpatterned, the DUV radiation used to image the photoresist reflects offthe surface of the underlying substrate. Silicon and aluminum, which arecommonly used in integrated circuit manufacture, are highly reflectiveto DUV light. The reflection from the surface of the underlyingsubstrate, together with the uneven topography of the underlyingsubstrate, produces an uneven distribution of light in the photoresistmaterial being imaged. This results in a large number of artifacts beingproduced in the resulting photoresist material.

In order to provide very high definition patterns with micron andsubmicron sized vias and channels, the number of artifacts producedduring photoresist patterning must be minimized. Recent advances inmicrolithography have demonstrated that including an antireflectivecoating (ARC) between the photoresist and the substrate can dramaticallyreduce the number of artifacts in the patterned photoresist. The use ofARCs in microlithographic processes are discussed at length in the priorart. Horn, Solid State Technology, pp. 57-62, November, 1991, disclosesthat resolution better than 0.5 μm using optical lithography isdependent upon two critical processes: ARCs and planarization. Theproblem of reflective notching of a photoresist material resulting fromlight reflection from an aluminum component on a silicon substrate isspecifically discussed in Horn. U.S. Pat. No. 4,609,614 to Pampalone etal. describes the use of multifunctional acrylates, methacrylatemonomers, a dye, and a photoinitiator to produce an absorptive layer foroptical lithography. In Pampalone et al., the photoresist layer used forpatterning the substrate overlies the absorptive layer. U.S. Pat. No.4,910,122 to Arnold et al. discloses an ARC interposed underphotosensitive layers which includes a light absorbing dye. U.S. Pat.No. 5,126,289 to Ziger which discusses spinning on an ARC of at leastthree times the thickness of the largest surface irregularity so thatthe substrate/ARC combination is planar prior to photoresistapplication. U.S. Pat. No. 5,234,990 to Flaim et al. discloses the useof a polysulfone and polyurea polymers as an ARC.

There is a need for ARC materials which have inherent light absorbingproperties provided by monomers in the polymer backbone. Prior artcompositions that include dyes dispersed in a polymer carrier have thedisadvantage that an extra processing step to evenly distribute the dyethroughout the polymer is required, and the disadvantage that smallnon-uniformities in dye distribution may result in non-uniformanti-reflective properties. In addition, small molecule or monomericdyes have a tendency to leach out during over coating with thephotoresist solution. Because the thickness of the ARC layers should bekept as small as possible, slight non-uniformities in the ARC canadversely affect the patterning results. The polyurea and polysulfonepolymers described in U.S. Pat. No. 5,234,990 to Flaim et al. have theadvantage of some inherent light absorptive ability provided by thepolymer backbone. However, these materials may not be suitable for usein many patterning processes. Thus, it would be advantageous to identifyalternative polymers that are useful as ARCs.

SUMMARY OF THE INVENTION

It is an object of this invention to identify a new polymer useful as anARC.

According to the invention, a co-polymer of a benzophenone andbisphenol-A has been found to have a high absorbance at 248 nm. Thus,this co-polymer will be useful as an ARC in microlithographyapplications. Including monomers with the anthracene moiety in thepolymer backbone can enhance the absorbance at 248 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, aspects and advantages will be betterunderstood from the following detailed description of the preferredembodiments of the invention with reference to FIG. 1 which is a graphshowing the linewidth variation which results when photoresists arepatterned with and without the benzophenone/bisphenol-A co-polymer beingused as an ARC.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

A co-polymer formed from a benzophenone and bisphenol A having theformula: ##STR1## where x is greater than 1. Co-polymers having amolecular weight between 10k and 80k have been found to have idealcharacteristics for use as an ARC. The co-polymer is formed by acondensation reaction of 4,4'-isopropylidine diphenol (bisphenol Amonomers) and 4,4'-dihalobenzophenones (benzophenone monomers).

The bisphenol A monomer having the formula: ##STR2## provides theco-polymer with solubility characteristics that allow the co-polymer tobe dissolved or dispersed in a suitable carrier or solvent such ascyclic ketones (e.g., cyclopentanone or cyclohexanone). Polymers basedon 4,4'-methylene diphenol (biphenol), as opposed to bisphenol-A, areinherently less soluble because of the lack of main chain flexibilitythat the isopropylidene structure imparts to the polymer (e.g., polymersbased on biphenol are more easily crystallized). Solubility in a carrieris important to an ARC material since it will typically be applied to asubstrate by spin coating, dip coating or other suitable processes, andit is essential that the coating process evenly distribute the ARCmaterial across the substrate surface. However, the ARC polymer mustalso be impermeable and insoluble to typical resist casting solvents(e.g. proplyene glycol, monomethyl ether acetate, ethyl lactate, anddiglyme).

The benzophenone monomer, which has a leaving group such as a halogen orthe like which condenses with the hydroxyl group of the bisphenol-A,provides the co-polymer with inherent DUV absorptive properties.Preferably, the benzophenone monomer is either 4,4'dichlorobenzophenoneor 4,4'-difluorobenzophenone as set forth below in the followingstructures: ##STR3## The benzophenone has particularly strong absorptionat 248 nm. Thus, the co-polymer produced will be be particularly usefulas an ARC for patterning a photoresist at 248 nm.

While the bisphenol A monomers have been described above as havinghydroxy (--OH) functional groups connected to the phenyl rings and thebenzophenone monomers have been described above as having halogenfunctional groups (e.g., --Cl --F, etc.), it is to be understood thatthe functionality could be reversed and the co-polymer produced would beidentical. Thus, within the practice of this invention, bisphenol Amonomers include both 4,4'-isopropylidine diphenol and 4,4'-dihaloisopropylidene diphenyl, and benzophenone monomers include bothdihalobenzophenones and dihydroxybenzophenones.

The co-polymer is ideally produced from a composition that includes1-50% of the bisphenol A monomer and 50-99% of the benzophenonemonomers. Greater quantities of benzophenone monomers than bisphenol Amonomers can be included in solution by using both dihalobenzophenonesand dihydroxybenzophenones in combination with bisphenol A monomers. Inthis way, the benzophenone monomers can condense with each other as wellas the bisphenol A monomers. It should be understood that both types ofbisphenol A monomers (4,4'-isopropylidene diphenyl and 4,4'dihaloisopropylidene diphenyl) can also be present in solution.

It has also been determined that including other chromophores besidesthe benzophenone in the polymer backbone can result in enhancedabsorptive properties. In particular, 9,10-dichloromethylanthracene,which has the formula: ##STR4## has strong absorption at 248 nm.Combining 9,10-dichloromethylanthracene with the benzophenone andbisphenol A monomers will result in a condensation co-polymer having thegeneral formula: ##STR5## where m, n, and o reflect the relativepercentages of monomer constituents in the composition and n equals thesum of m and o. Similar to the discussion above, the anthracene monomercan have hydroxy functionality instead of the halogen (chlorine)functionality indicated above. Thus, anthracene monomers may be joinedwith other anthracene monomers as well as both types of benzophenonemonomers and both types of bisphenol A monomers. Also, similar to thediscussion above, the sum of the benzophenone monomers plus anthracenemonomers is preferably 50-99 wt % of the composition and the bisphenol Amonomers are preferably 1-50% by weight. In co-polymers which includethe anthracene monomer, it has been found to be preferable toincorporate the anthracene monomer at a rate of 1-20% into theco-polymer. Thus, a composition including 1-20% anthracene. monomer,1-50% bisphenol A monomer, and 1-49% benzophenone monomer yields anideal co-polymer for use as an ARC, and which has particularly strongabsorption at 248 nm.

The co-polymers, which include both the bisphenol A/benzophenone and thebisphenol A/benzophenone/anthracene, can be terminated by a variety ofendcapping agents. The endcapper preferably includes a halogen or otherleaving group which condenses with the phenolic moiety on the bisphenolA monomer. The terminating groups may be selected to provide theco-polymer with properties tailored to specific applications. Forexample, when the condensation polymer is terminated with an acid, suchas acetic acid, the polymer will be endcapped with hydroxy substituents.Formulating the co-polymer with an acidic endcapper allows theincorporation of reactive alkoxy silanes into the polymer for adhesionpromotion. This is accomplished by the reactive phenolic polymer chainends coupling with the silane additives. Haloalkanes (C_(n) H.sub.(2n+1)X) may also be employed as endcappers for the co-polymer. Haloalkaneswill produce an alkyl ether endcapped polymer that may exhibit increasedstability due to its chemical neutrality. Haloalkylanthracenes, such aschloromethylanthracene, may also be used as endcappers. As discussedabove in connection with the incorporation of anthracene monomers intothe polymer backbone, using an anthracene endcapper for the co-polymerwill provide the polymer with increased absorbance in the DUV at 248 nm.Haloalkyl coumarins, which are lactones, may also be used as endcappingagents. The haloalkyl coumarins have absorbance properties at 365 nm;thus, the co-polymer produced could be tailored to absorb light at twodifferent wavelengths if haloalkyl coumarins were used as endcappers.Specifically, the benzophenone and anthracene monomers in the polymerbackbone would absorb at 248 nm, and the alkylcoumarin endcappers wouldabsorb at 365 nm. Haloalkyl aromatic azides may also be utilized asendcappers for terminating the co-polymer. Incorpation of the azide asan endcapper would allow the co-polymer chains to crosslink upon hightemperature heating to produce a stable thermoset.

A typical formulation used as an ARC in the practice of the presentinvention would preferably include up to 25 wt % co-polymer in 75 wt %or more of a carrier fluid or solvent such as cyclic ketones and/orgamma butyrolactone (GBL). Other solvents which are capable ofdissolving the polymer may also be useful within the practice of theinvention. Other agents such as alkoxy silanes and aromatic azides mayalso be included to promote adhesion and cross-linking/stability. Itshould be understood that the weight percentages of co-polymer, carrierfluid, and other constituents can vary widely depending on the needs ofthe fabricator. An exemplary composition could include the following:

(1) co-polymer 0-15 wt %;

(2) cyclic ketone and/or GBL 75-100 wt %;

(3) alkoxy silane 0-3%; and

(4) aromatic azide 0-20%.

The ARC composition would be applied to the suface of the substrateunderneath a photoresist material to be patterned. Preferably, thethickness of the ARC composition would be two or three times the size ofany imperfections on the substrate surface. The ARC composition wouldenhance microlithography of the overlying photoresist by absorbing DUVradiation, particularly at 248 nm.

EXAMPLE

The ability of the co-polymer of the present invention to reducelinewidth variation upon patterning a photoresist with DUV has beentested. In the experiment, a control set of six wafers was coated withvarying thicknesses of a deep-UV, chemically amplified photoresist. TheDUV photoresist used was APEX-E which is commercially available fromShipley Co. The wafers were patterned with a 0.37 NA Canon Excimerstepper to produce a series of 0.5 μm lines and spaces. The linewidthvariation with respect to varying photoresist thickness is shown belowin Table 1.

    ______________________________________                                        Film Thickness (Å)                                                                        Linewidth (μm)                                             ______________________________________                                        8175            0.47                                                          8350            0.41                                                          8630            0.53                                                          8890            0.45                                                          9340            0.54                                                          9820            0.47                                                          ______________________________________                                    

A second set of six wafers was coated with 800 Å of a co-polymer ofbenzophenone and bisphenol A, and baked at 200° C. for 60 seconds. Thewafers were then coated with various thicknesses of the same chemicallyamplified photoresist which was used in the control group. The waferswere then exposed in the same fashion as the control wafers. The resultsare shown in table 2.

    ______________________________________                                        Film Thickness (Å)                                                                        Linewidth (μm)                                             ______________________________________                                        8360            0.51                                                          8690            0.49                                                          8775            0.52                                                          9350            0.49                                                          9790            0.53                                                          9975            0.50                                                          ______________________________________                                    

FIG. 1 graphically presents the data on linewidth variation from Tables1 and 2. The wafers pre-coated with the co-polymer clearly have lessline-width variation than the uncoated wafers.

While the invention has been described in terms of its preferredembodiments, those skilled in the art will recognize that the inventioncan be practiced with modification within the spirit and scope of theappended claims.

We claim:
 1. A method of patterning a photoresist material with deepultraviolet radiation, comprising the steps of:applying a co-polymercomprised of bisphenol A monomers and benzophenone monomers to a surfaceof a substrate; applying a photoresist over said co-polymer; andpatterning said photoresist with deep ultraviolet radiation, saidco-polymer reducing reflected deep ultraviolet radiation from saidsurface of said substrate.
 2. The method of claim 1 wherein saidco-polymer includes anthracene monomers.
 3. The method of claim 2wherein said co-polymer is terminated with a moiety selected from thegroup consisting of hydroxy, alkyl ether, alkyl anthracene, alkylcoumarin, alkyl aromatic azide, and alkoxy silane.